CN101400492A - Optical film and method for producing same - Google Patents

Abstract

Disclosed is a method for producing an optical film composed of a transparent resin and a metal oxide, which film has high light transmittance and light diffusion property even it is formed thin. Also disclosed is such an optical film. Specifically disclosed is a method for producing an optical film having a total light transmittance of not less than 70% and a haze value of not less than 20%, which comprises a step (A) wherein a metal compound which forms a metal oxide through a sol-gel reaction is subjected to a sol-gel reaction in a solvent; a step (B) for preparing a solution containing a transparent resin as a solute; a step (C) for mixing the mixture obtained in the step (A) with the solution obtained in the step (B); and a step (D) wherein the mixture obtained in the step (C) is coated or spread over a substrate or container and then heated for evaporating the solvent, thereby forming a film thereon.

Description

Blooming and manufacture method thereof

Technical field

The present invention relates to blooming and manufacture method thereof.

Background technology

In LCD,, be to display picture by the LGP leaded light from the light that cold-cathode tube (being generally fluorescent lamp) sends.At this moment, in order not produce the even phenomenon of luminance nonuniformity, and be used to make the optical diffusion film of the briliancy homogenization of picture integral body.The requirement optical diffusion film has: make the light diffusion of being sent by light source, the function that does not manifest the picture of light source; Do not damage the lightness of light source and keep the function of the briliancy of picture integral body.Thereby, require optical diffusion film have will by reflection or absorb the loss produced be suppressed to Min., make scattered light by and character that directional light is passed through.

In the past, as optical diffusion film, used the material of the surface of transparent sheet such as glass, acrylic resin, Merlon, polyester or film being made inferior light shape.In addition, also use the transparent sheet or the film of inorganic particles such as being added with calcium carbonate, silicon dioxide granule or transparent resin particles such as polystyrene, PMMA.In addition, (for example, patent documentation 1～3) such as materials of also using the resin that will be added with described particle on the surface of transparent sheet etc. to be arranged to film.

In recent years, with regard to LCD, than requiring high briliancyization and slimming in the past more consumingly.Therefore, require to have simultaneously the haze value of good light transmittance and proper range for the optical diffusion film of LGP mode, and the material that approaches of thickness.

As optical diffusion film, the known photodiffusion material that has in polymer (in the organic polymer) to disperse the size metal oxide bigger than visible wavelength region.For example, in patent documentation 4, the photodiffusion material of the metal oxide particle that has disperseed to have the refractive index different with polymer in polymer is disclosed.This material is by described mix particles such short-cut method in polymer is obtained.But, added the photodiffusion material of the metal oxide particle of particle diameter almost single (particle diameter is distributed as single dispersion), exist the scattering efficiency height of specific wavelength, the optical colour that sees through such present wavelength dependency (with reference to " オ プ テ イ カ ル You Machine polymer Cai Liao development ying Yong Ji Intraoperative (the Application and Development technology of optics organic polymer material) ", problem p183).In addition, just merely metal oxide particle is mixed in the polymer, also has the problem of the aggegation be difficult to suppress particle.

On the other hand, as the aggegation that in polymer, suppresses inorganic compound particles and make its dispersion and obtain the method for complex, the known method (with reference to patent documentation 5, non-patent literature 1 etc.) that has the sol-gel process utilized to obtain the polymer-metal oxide complex.Said sol-gel process is to make the polycondensation reactions that are hydrolyzed (sol gel reaction) such as metal alkoxide, metal acetylacetonate compound, metal carboxylate make the method for metal oxide.Sol-gel process can be with lower temperature synthesis of metal oxide in solution, and therefore, known is to be suitable for and the method for resolvent compoundization of organic material at high temperature.In addition because sol-gel process can come synthesis of metal oxide by the reaction of molecular level, therefore, can be in polymer the metal oxide of dispersing nanometer level particle diameter.Because such characteristic is used as the method for the nano composite material of making metal oxide and transparent resin material especially.Such nano composite material is known as does not usually lose the transparency, and has improved thermal characteristics and mechanical property, for various resins a lot of report examples is arranged.

As the example that utilizes above-mentioned sol gel reaction, the following excellent organic mineral complex blooming of the transparency that obtains is arranged:, make metal alkoxide based compound etc. carry out sol gel reaction and obtain (patent documentation 6) to be the state of equal solvent in acid amides system or urea with polymer dissolution.

In addition, in patent documentation 7, following method being disclosed: after making metal alkoxide become be produced concentration gradient by impregnation in polymer, makes metal alkoxide carry out polycondensation reaction (sol gel reaction).The particle diameter that the polymer-metal oxide complex that obtains with this method just becomes metal oxide has the structure of gradient on the thickness direction of film.

Patent documentation 1: the real fair 3-26481 communique of Japan

Patent documentation 2: TOHKEMY 2004-198743 communique

Patent documentation 3: TOHKEMY 2005-55861 communique

Patent documentation 4: TOHKEMY 2003-109747 communique

Patent documentation 5: Japanese kokai publication hei 8-73739 communique

Patent documentation 6: TOHKEMY 2005-264038 communique

Patent documentation 7: Japanese kokai publication hei 9-87526 communique

Non-patent literature 1: make flower Ji husband work, " ゾ Le-ゲ Le method ying is used (application of sol-gel process) ", ア グ ネ holds wind society, 1997

Summary of the invention

The problem that invention will solve

Disclosed in the patent documentation 1～3, with the method for Surface Machining Cheng Yaguang shape, be to adopt to carry out sandblast processed mould or embossing roller for machining to the concavo-convex method of film surface transfer printing.But this method is difficult to be applied to make the film of the following thickness of 50 μ m.This is because the intensity of the film self of film does not tolerate this processing, and distortion such as generation warpage.In addition, with regard to LCD,, when using, damage prism sometimes in that this face is contacted with prismatic lens with the blooming of Surface Machining Cheng Yaguang shape.Therefore, cause the problems such as optically focused reduction of light sometimes.

In addition, the particle disclosed in the patent documentation 4, that refractive index is different makes an addition in the methods such as transparent thin slice or film inside, exists by the problem that produces wavelength dependency in the diffused light of the aforementioned film that obtains.In order to improve this problem, can on the cross-wise direction of film, make the change of size of metal oxide.But, if just merely in polymer, mix the particle of the different metal oxide of particle diameter, then can not make the particle diameter gradient-structure, and because particles aggregate, so be difficult to solve the problem of wavelength dependency.

In addition, if just simple in polymer the particle of mixed-metal oxides, the flatness when then being difficult to guarantee to make film.In order to make the thickness attenuation, and prevent that metal oxide particle is outstanding on the film surface, and do not damage surface smoothing, need to use metal oxide particle enough little concerning thickness.But if the particle diameter of metal oxide is little, then scattering efficiency just reduces.Further, because particle diameter just is easy to generate aggegation between the small-particle more more, therefore, the light diffusing and the homogeneity thereof of film also have problems.

Disclosed sol-gel process in patent documentation 5 and the non-patent literature 1 is to suppress metal oxide aggegation and make the method for its dispersion in polymer as previously mentioned.But this method is originally for this particle is scattered in the polymer with nanoscale and develop.The complex that the metal oxide that obtains with this method is scattered here and there with nanoscale in polymer be transparent and the light diffusion effect not high, therefore be not suitable for use in being used for the blooming of light diffusion.

Usually, in order to bring into play sufficient light diffusion effect, need metal oxide with the particle size dispersion of sub-micron degree in polymer.Adopt the method for putting down in writing in these documents, obtain making the above big or small metal oxide of sub-micron to be scattered in the method for the complex in the polymer, do not reporting as yet before this.Its reason may be, if the particle diameter of metal oxide more than sub-micron, the transparency of complex will be lost, and then the raising effect of thermo-mechanical property also can diminish.In addition, even because the metal oxide of submicron-scale is pulverized also making easily by sintering, therefore, adopt the necessity of sol-gel process also little.The method of record in the patent documentation 6, its purpose also is with the nanoscale dispersing metal oxides, obtains transparent complex.That is, do not exist the employing sol-gel process to make the such design of blooming of light diffusing excellence.

On the other hand, the method for record in the patent documentation 7 is the method for the complex of the particle diameter that utilizes sol gel reaction to obtain metal oxide in the polymer structure that has gradient on the thickness direction of film.The purpose of this method is the complex that obtains the mechanical strength excellence, and is not documented in the application in the optical applications fully.In addition, the complex procedures of this method.In addition, the material according to this method obtains because thermal coefficient of expansion produces difference on thickness direction, therefore exists according to problems such as variations in temperature film generation warpages.Infer that its reason is: the metal oxide that is present in the film has concentration gradient, therefore the volume fraction difference of the metal oxide on thickness direction.

That is, require blooming to be film and surface smoothing excellence, to have high full light permeability, also to have high light diffusing simultaneously, still, also do not propose to obtain the method for such film before this.In addition, require blooming to have high light diffusing, do not have the wavelength dependency of diffused light and for its shape stability excellence of variations in temperature, still, such film does not exist before this.

Thereby, the purpose of this invention is to provide a kind of manufacture method of blooming, this blooming is film and surface smoothing excellence, have high full light permeability, also have high light diffusing simultaneously.Further, the purpose of this invention is to provide and a kind ofly have high light diffusing, do not have the wavelength dependency of diffused light and for the blooming of its shape stability excellence of variations in temperature.That is, the manufacture method by following blooming of the present invention solves above-mentioned problem.

[1] a kind of manufacture method of blooming wherein, comprising: (A) will generate the metallic compound of metal oxide by sol gel reaction, and carry out the operation of sol gel reaction in solvent; (B) preparing with the transparent resin is the operation of the solution of solute; (C) mixture that will in described (A) operation, the obtain operation of mixing with the solution that in (B) operation, obtains; And the mixture that (D) will obtain in described (C) operation is after coating on substrate or the container or launching, and heats the operation that solvent is evaporated form film, and the total light transmittance of this blooming is more than 70%, and haze value is more than 20%.

[2], wherein, before described (D) operation, further comprise and make the described metal oxide that exists in the mixture that in (C) operation, obtains carry out the operation of sol gel reaction according to the manufacture method of [1] described blooming.

[3] a kind of manufacture method of blooming wherein, comprising: (E) preparing with the transparent resin is the operation of the solution of solute; (F) in the solution that in described (E) operation, obtains, mix the metallic compound that generates metal oxide by sol gel reaction, and carry out the operation of sol gel reaction; And the mixture that (G) will obtain in described (F) operation is after coating on substrate or the container or launching, and heats the operation that solvent is evaporated form film, and the total light transmittance of this blooming is more than 70%, and haze value is more than 20%.

[4] manufacture method of basis [3] described blooming, wherein, before described (G) operation, further comprise in the mixture that in (F) operation, obtains, mixing generates metallic compound, solvent, water or the catalyst of metal oxide by sol gel reaction, and carries out the operation of sol gel reaction.

[5] according to the manufacture method of each described blooming in [1]～[4], wherein, described (D) or film making process (G) comprise the operation of the particle growth that makes the metal oxide that generates by described sol gel reaction.

[6] according to the manufacture method of [5] described blooming, wherein, the operation that the described particle that makes metal oxide is grown up is to make described particle diameter change the operation of growing up with respect to the thickness direction gradient ground of described blooming.

[7] manufacture method of each described blooming in basis [1]～[6], wherein, described transparent resin is polyimides, Merlon, polyacrylate, polymethacrylates, polyether-ketone, polyether-ether-ketone, polystyrene, polyester, epoxy resin, polyamide, polysulfones, Nomex, polyurethane, polyvinyl acetate, polyvinyl alcohol or polyacrylic acid.

[8] according to the manufacture method of each described blooming in [1]～[7], wherein, described metallic compound by sol gel reaction generation metal oxide comprises silicon, titanium, zirconium or aluminium element.

[9] according to the manufacture method of each described blooming in [1]～[8], wherein, described metallic compound by sol gel reaction generation metal oxide is metal alkoxide, metal acetylacetonate compound, metal carboxylate or their condensation polymer.

[10] according to the manufacture method of each described blooming in [1]～[9], wherein, in described sol gel reaction,, use inorganic acid, organic acid, inorganic base or organic base as catalyst.

[11] according to the manufacture method of each described blooming in [1]～[10], wherein, described (D) operation or (G) operation be 40～180 ℃ down heating made the operations of solvent evaporation in 1～50 hour.

[12] manufacture method of each described blooming in basis [4]～[11], wherein, solvent that uses in described (A) operation or the solvent that is mixed in the mixture that obtains in described (F) operation are water, N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, DMSO, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, THF, diox, methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, methyl cellosolve or ethyl cellosolve.

[13] manufacture method of each described blooming in basis [1]～[12], wherein, described metallic compound by sol gel reaction generation metal oxide is included in the metal alkyl alkoxide that has alkyl and alkoxyl in the molecule, and described is that the solvent of the solution of solute comprises water with the transparent resin.

[14] according to the manufacture method of each described blooming in [1]～[13], wherein, described blooming is an optical diffusion film.

[15] a kind of blooming that produces by each described method in [1]～[13], wherein, thickness is below the 30 μ m, and haze value is more than 70%.

[16] according to [15] described blooming, wherein, the centre plane roughness (Ra) of single or double is below the 100nm.

In addition, solve above-mentioned problem by following blooming of the present invention.

[17] a kind of blooming, it is scattered in blooming in the transparent resin for metal oxide, and wherein, on the thickness direction of this blooming, the particle diameter gradient of described metal oxide ground changes, and the volume fraction of this metal oxide does not change in fact.

[18] according to [17] described blooming, wherein, when the average grain diameter that is present in from a face to the per unit area of the described metal oxide of the scope of thickness 40% of described blooming is X, the average grain diameter of the per unit area of the described metal oxide of 40% scope is Y from another face to thickness, when X was bigger than Y, the particle diameter gradient that defines with X/Y was more than 1.2.

[19] according to [17] or [18] described blooming, wherein, when the volume fraction from a face to the described metal oxide of the scope of thickness 40% of described blooming is W, the volume fraction of the described metal oxide of 40% scope is V from another face to thickness, W is V when above, is below 2 with the volume fraction gradient of W/V definition.

[20] according to each described blooming in [17]～[19], wherein, described blooming is an optical diffusion film.

The invention effect

According to the present invention, a kind of total light transmittance can be provided is more than 70% and haze value is 20% blooming, and this blooming is the film of light diffusing excellence, and the surface smoothing excellence.In addition, the blooming that obtains by the present invention is: metal oxide is scattered in the transparent resin, on the thickness direction of this blooming, though the variation of the particle diameter gradient of described metal oxide ground,, its volume fraction there is no substantial variation.That is, can provide a kind of by the present invention and have high light diffusing, not have the wavelength dependency of diffused light and with respect to the blooming of its shape stability excellence of variations in temperature.

Description of drawings

Fig. 1 is the TEM image in the metal oxide cross section that is scattered in the blooming of the present invention in the transparent resin.

The specific embodiment

1. blooming of the present invention

The blooming that obtains in the present invention is to get according to method for making described later, and has that total light transmittance is more than 70%, haze value is the feature more than 20%.This film also is known as " particular optical rerum natura film ".

In addition, another blooming of the present invention is that metal oxide is scattered in the blooming in the transparent resin, it is characterized in that, on the thickness direction of this blooming, the particle diameter gradient ground of described metal oxide changes, and the volume fraction of this metal oxide does not change in fact.This film also is known as " gradient-structure film ".

Said blooming is meant the membrane-like member of using in optical applications such as display material.In addition, blooming of the present invention also can be an optical diffusion film.Said optical diffusion film is in display board etc., the light that sends by light source by LGP by leaded light when the display picture, make the member of the briliancy homogenization of picture integral body for the phenomenon that does not produce luminance nonuniformity.

1-1 is about particular optical rerum natura film

Particular optical rerum natura film is characterised in that, by the following method (below, be called " first method ") to make, this manufacture method comprises: (A) will generate the metallic compound of metal oxide by sol gel reaction, and carry out the operation of sol gel reaction in solvent; (B) preparing with the transparent resin is the operation of the solution of solute; (C) mixture that will in described (A) operation, the obtain operation of mixing with the solution that in (B) operation, obtains; And (D) will be at mixture that described (C) operation obtains after coating on substrate or the container or launching, heat the operation that solvent is evaporated form film.

In addition, described particular optical rerum natura film is characterised in that, by the following method (below, be called " second method ") to make, this manufacture method comprises: (E) preparing with the transparent resin is the operation of the solution of solute; (F) in the solution that obtains by described (E) operation, make the operation of carrying out sol gel reaction by the metallic compound of sol gel reaction generation metal oxide; And the mixture that (G) will obtain in described (F) operation is after coating on substrate or the container or launching, and heats the operation that solvent is evaporated form film.

(1) optical characteristics

Said total light transmittance is the parallel light that sees through that light by the incident light that incides sample, incident spreads in sample and the diffusion that sees through sees through light and keeps straight on and see through along incident direction, represents with following formula.

" total light transmittance " (%)=(" diffusion see through light "+" the parallel light that sees through ")/" incident light " * 100

By following formula as can be known, said total light transmittance height, mean the light that comprises diffusion, see through the situation of light easily.

Said haze value is the value in order to the following formula subrepresentation, becomes the index of light diffusivity.

" haze value " (%)=" diffused light transmitance "/" total light transmittance " * 100

Wherein, diffused light transmitance (%)=" diffusion sees through light "/" incident light " * 100

From following formula as can be known, said haze value height means to see through and spreads the high situation of ratio that sees through light in the light.

The total light transmittance of particular optical rerum natura film of the present invention is more than 70%, haze value is more than 20%.The haze value of this film is preferably more than 20% and less than 100%, more preferably more than 50%, below 95%.This is because the light diffusing excellence.

That is, what particular optical rerum natura film of the present invention had is characterized as: total light transmittance height, and in the transmitted light is not parallelly to see through light but diffusion sees through the light height, that is to say light diffusing height (light diffusing excellence).

(2) transparent resin

Certain optical properties film of the present invention contains transparent resin and is scattered in metal oxide particle in the transparent resin.Said transparent resin is when thickness is 15 μ m, the parallel rays transmitance that demonstrates wavelength 650nm is at the organic polymer more than 60% (polymer), be preferably demonstrate wavelength 650nm the parallel rays transmitance at the organic polymer more than 70% (polymer).

The transparent resin that uses among the present invention is preferably has deliquescent resin to the water or the solvent that can mix with water.As described later, it is in the solution of solute that the manufacture method of this film is included in the transparent resin, makes the operation of carrying out sol gel reaction by the metallic compound of sol gel reaction generation metal oxide.This be because, owing in sol gel reaction, make water sometimes, therefore, if the solute of described solvent be water or can mix with water, then carry out sol gel reaction easily.The example of such transparent resin comprises polyimides, Merlon, polyacrylate, polymethacrylates (PMMA), polyether-ketone, polyether-ether-ketone, polystyrene, polyester, epoxy resin, polyamide, polysulfones, Nomex, polyurethane, polyvinyl acetate, polyvinyl alcohol (PVA), polyacrylic acid.

(3) metal oxide

The metal oxide that uses in particular optical rerum natura film is so long as the material that can adopt sol-gel process to generate just is not particularly limited.These examples comprise the oxide of lithium, sodium, copper, calcium, strontium, barium, zinc, boron, aluminium, gallium, yttrium, silicon, germanium, lead, phosphorus, antimony, vanadium, tantalum, tungsten, lanthanum, neodymium, titanium or zirconium.Wherein, in order to improve the light diffusing energy, preferably use the oxide of silicon, zirconium, titanium or aluminium.

The content of the metal oxide in the particular optical rerum natura film is preferably 0.1～70 mass parts with respect to the transparent resin of 100 mass parts and the complex of metal oxide, more preferably 0.1～50 mass parts.This is because the mechanical strength excellence of light scattering effect and film.Here the content of said metal oxide is meant, the blooming that will be made of the complex of transparent resin and metal oxide burns till residual thereafter ash content under 800 ℃ in air.

In order to satisfy specific optical characteristics, preferably consider from the angle of refringence, select the metal oxide and the transparent resin that use in the particular optical rerum natura film.Poor (difference of the refractive index of metal oxide and the refractive index of transparent resin) of this refractive index is preferably 0.02～1.40, and more preferably 0.04～1.30.Such preferred example comprises that transparent resins such as polymethyl methacrylate, polyvinyl alcohol or polyimides and metal oxide are the combination of metal oxides such as silica or titanium oxide.

(4) particle diameter of metal oxide and particle diameter gradient

The particle diameter of the metal oxide in the particular optical rerum natura film is preferably the scope of 0.001 μ m～100 μ m, more preferably the scope of 0.01 μ m～20 μ m.During in particular as optical diffusion film, above-mentioned particle diameter is preferably 0.03 μ m～15 μ m.This is because can satisfy above-mentioned optical characteristics, and the flatness excellence on film surface.In addition, when in film, having the metal oxide particle that surpasses 15 μ m,, then can not damage the flatness of film, so preferred if this particle is not present in the film surface and is present in film inside.

But under the certain state of metal oxide content, if increase its particle diameter, then the number of particle reduces.The light diffusing of such blooming reduces sometimes.That is, the particle diameter of the metal oxide in the particular optical rerum natura film is affected because of the content of metal oxide, and therefore, this particle diameter considers also that preferably the content of metal oxide regulates.

The form of the metal oxide in the particular optical rerum natura film and size thereof can be measured by transmission electron microscope (TEM), SEM (SEM), AFM (AFM) or X ray scattering.Metal oxide of the present invention is to exist with the form that is separated with transparent resin, and its shape is various.This metal oxide owing to generate by sol gel reaction in polymer as described later, is indefinite shape often therefore.

In addition, the metal oxide in the particular optical rerum natura film is preferably with the thickness direction with respect to film, and the mode that the particle diameter gradient of this metal oxide particle ground changes exists.The metal oxide particle diameter that is present in the film is called as " particle diameter gradient " with respect to the gradient variation of film thickness direction.Specifically, the particle diameter gradient is the average grain diameter of the metal oxide particle that existed by the unit are from the two-sided scope to thickness 40% of film, defines as described below.The average grain diameter X that is present in from a face of film to the particle of thickness 40% (as the X zone) is measured, the average grain diameter Y that is present in the particle in (as the Y zone) from another face to same range as is measured.X/Y is defined as particle diameter gradient (wherein, X is greater than Y).In this film, the big and little particle diameter gradient of the opposing party of the average grain diameter that is preferably the wherein side in X zone and the Y zone.Particle diameter gradient in this film is preferably 1.2～100000, and more preferably 1.5～50000, more preferably 1.6～10000.

Described average grain diameter, two-sided to the scope of thickness 40% at film is 1～10000 μ m in unit are preferably ², 5～5000 μ m more preferably ², be preferably 10～2500 μ m especially ²Scope in calculate.Average grain diameter can adopt image analysis software (Image-Pro Plus, Planetron company makes) to wait and obtain by the image that for example obtains by tem observation.

(5) volume fraction of metal oxide

The volume fraction of the metal oxide in the particular optical rerum natura film preferred film does not change in fact on film thickness direction.This be because, the film of this structure, thermal coefficient of expansion does not have difference on thickness direction, can be owing to variations in temperature etc. produces warpage.Described volume fraction is tried to achieve as follows.At first, tem observation is carried out in the blooming cross section, the image that obtains is carried out graphical analysis, obtain the summation of the area that is present in the metal oxide particle in the unit are.Then, obtain area occupation ratio with this area divided by unit are.To change this area occupation ratio and be defined as volume fraction.In graphical analysis, preferably use aforesaid image analysis software (Image-Pro Plus:Planetron company).Unit are is preferably 1～1000 μ m ², 5～500 μ m more preferably ², further be preferably 10～250 μ m ²

Said volume fraction on film thickness direction does not change in fact, means that the volume fraction gradient as giving a definition is approximately 1.The volume fraction of the described metal oxide the scope from a face to 40% (X zone) of described blooming is made as W, and will be made as V from the volume fraction of the described metal oxide the scope (Y zone) of another face to 40% time, the volume fraction gradient is represented with W/V (wherein, W is more than the V).The volume fraction gradient of blooming of the present invention is preferably below 2, and more preferably 1.0～1.5.This is the warpage owing to the film that can reduce to produce because of variations in temperature etc.

(6) surface smoothing of film

The surface roughness of particular optical rerum natura film is come in centre plane roughness Ra, is preferably below the 100nm.This is because if the surface smoothing reduction of film, during then with other film-stack, damages other film sometimes.For example, when particular optical rerum natura film is used as the optical diffusion film that uses in LCD,, then damage prismatic lens sometimes if surface smoothing is low.Thereby, by making Ra, when particular optical rerum natura film and other member are used in combination, can under the situation of not damaging other members, use in described scope.

(7) thickness of film

The thickness of particular optical rerum natura film of the present invention is preferably 5～500 μ m, 8～300 μ m more preferably, and more preferably 10～100 μ m are preferably 10～30 μ m especially.This is because when being used for display unit etc., slimming that can implement device.

Particular optical rerum natura film of the present invention is with regard to optical characteristics, surface smoothing, thickness, and preferred thickness is that 30 μ m are following, haze value is more than 70%, and more preferably thickness is that 30 μ m are following, haze value is more than 70% and Ra is below the 100nm.

1-2 gradient-structure film

Gradient-structure film as another blooming of the present invention is that metal oxide is scattered in the blooming in the transparent resin, what it had is characterized as: on the thickness direction of this blooming, the particle diameter gradient ground of described metal oxide changes, and the volume fraction of this metal oxide does not change in fact.This blooming can be an optical diffusion film.

(1) each composition

In the transparent resin and metal oxide that in the gradient-structure film, uses, can use and the same material of particular optical rerum natura film.There is no particular restriction for the content of metal oxide, but preferred according to doing like that of narrating in particular optical rerum natura film.

(2) the particle diameter gradient and the volume fraction of metal oxide

Being characterized as of gradient-structure film: on its thickness direction, the particle diameter gradient of described metal oxide ground changes.The gradient variation of said this particle diameter is the identical meaning with " the particle diameter gradient " narrated in particular optical rerum natura film.The value of this particle diameter gradient also is preferably as narrating in the particular optical rerum natura film.In addition, about volume fraction, also be preferably identical with particular optical rerum natura film.

(3) optical characteristics

The optical characteristics of gradient-structure film so long as the characteristic that satisfies as blooming get final product, and unrestrictedly.Wherein, preferred haze value is more than 20% and less than 100%, is preferably more than 70% especially.This is because light diffusivity excellence.

(4) surface smoothing, thickness

The surface smoothing of gradient-structure film and thickness are preferably according to doing like that of narrating in particular optical rerum natura film.

Particularly, the gradient-structure film is with regard to optical characteristics, surface smoothing, thickness, and preferred haze value is 70% or more, Ra is below the 100nm and thickness is below the 30 μ m.

2. about the manufacture method of blooming

Above-mentioned particular optical rerum natura film is made by first method that comprises (A)～(D) or second method that comprises (E)～(G) as mentioned above.In addition, the gradient-structure film can at random be made, but preferably makes by preceding method.Below, the manufacture method as particular optical rerum natura film and gradient-structure film (merge them sometimes and be called " blooming of the present invention ") illustrates first and second manufacture method.

This manufacture method is divided into and comprises (A)～(C) or (E)～(F) " regulating the operation of film with mixture ", and comprises (D) or (G) " film making process " two parts.Thereby, every part operation is described.

1-1 regulates the operation of film with mixture

In the present invention, said sol gel reaction is meant, with the functional groups such as alkoxyl of metallic compound by acid or base catalyst be hydrolyzed the reaction that generates hydroxyl (below, be called " hydrolysis "), and with the dewater reaction (below, be called " polycondensation reaction ") of polycondensation of the hydroxyl of the metal hydroxides that generates.

The A operation of (1) first method

The metallic compound that sol gel reaction generates metal oxide that passes through that uses in this operation is meant, can sol gel reaction take place and is changed to the compound of metal oxide.Metallic compound is the structure that is combined with functional group on metallic atom.Below, abbreviate this metallic compound as " metallic compound " sometimes.

By the metallic atom of metallic compound, the metal oxide in the blooming of determining finally to obtain.Preferred metal oxide as previously mentioned in blooming of the present invention.Thereby, in the above-mentioned metallic compound,, preferably contain lithium, sodium, copper, calcium, strontium, barium, zinc, boron, aluminium, gallium, yttrium, silicon, germanium, lead, phosphorus, antimony, vanadium, tantalum, tungsten, lanthanum, neodymium, titanium or zirconium as metallic atom.During for example as optical diffusion film, as previously mentioned, metallic compound preferably contains silicon, zirconium, titanium, aluminium as metallic atom.

Be combined with in the example of metallic compound of functional group at above-mentioned metal, comprise metal inorganic compounds such as metallo-organic compound such as metal alkoxide, metal acetylacetonate compound, metal carboxylate or metal nitrate, metal oxychloride, metal chloride (with reference to " science of sol-gel process " of making flower Ji husband work, ア グ ネ holds wind person, p17).In the present invention, can use them separately, also can make up 2 kinds with on use.In addition, also can use their functional group of a part carried out polycondensation and condensation polymer (being also referred to as " partial hydrolysis polycondensation compound ").

The object lesson of metal alkoxide comprises following material.Tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, tetraisopropoxysilan, MTMS, MTES, methyl tripropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, the n-pro-pyl trimethoxy silane, the n-pro-pyl triethoxysilane, the isopropyl trimethoxy silane, the isopropyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, the trifluoromethyl trimethoxy silane, the trifluoromethyl trimethoxy silane, vinyltrimethoxy silane, VTES, phenyltrimethoxysila,e, phenyl triethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, to the styryl trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, the 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-triethoxysilicane, the 3-chloropropyl triethoxysilane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-NCO propyl-triethoxysilicane, the tetramethoxy titanium, purity titanium tetraethoxide, titanium isopropoxide, butoxy aluminium, four n-butoxy zirconiums, zirconium tetraisopropoxide, barium isopropoxide, ethyoxyl calcium etc.

The object lesson of metal acetylacetonate compound comprises acetylacetone,2,4-pentanedione zirconium, titanium acetylacetone, aluminium acetylacetonate, Indium Tris acetylacetonate or zinc acetylacetonate etc.Wherein, preferred acetylacetone,2,4-pentanedione zirconium, titanium acetylacetone, aluminium acetylacetonate.

The object lesson of metal carboxylate comprises lead acetate, stearic acid yttrium, barium oxalate.

In above-claimed cpd, alkoxy silanes such as preferred TMOS, TEOS, titanium isopropoxide, butoxy aluminium, four n-butoxy zirconiums, zirconium tetraisopropoxide.This is because reaction control easily.

In addition, the refractive index of the metal oxide in the blooming that finally obtains is by also regulating with the metallic compound with different metal atom.Comprise the combination of alkoxy silane and tetramethoxy titanium, purity titanium tetraethoxide, titanium isopropoxide, butoxy aluminium, four n-butoxy zirconiums, zirconium tetraisopropoxide, acetylacetone,2,4-pentanedione zirconium, titanium acetylacetone or aluminium acetylacetonate etc. in the example of such combination.

In this (A) operation, make described metallic compound in solvent, carry out sol gel reaction.In sol gel reaction, when having functional groups such as alkoxyl when metallic compound, carry out polycondensation reaction after preferably making hydroxyl at this metallic compound of hydrolysis and with alkoxyl.Therefore, also can add water as required.This water also can contain catalyst.

Above-mentioned reaction for example can be added the water that also can contain catalyst as required by in advance described metallic compound being dissolved in the solvent, at room temperature or be heated to set point of temperature and wait and carry out.At this moment, use two or more metallic compounds also passable as described above like that.Perhaps, also can make first metallic compound, second metallic compound carry out sol gel reaction earlier respectively after, they are mixed.And then also can make this mixture carry out sol gel reaction.

The solvent that in this reaction, uses, as long as can dissolve described metallic compound, and unrestricted.But be the solvent that mixes or identical solvent preferably with the solvent that in (B) described later operation, uses, use in the modulation of transparent resin as the solution of solute.The example of this solvent comprises water, N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, DMSO, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, THF, diox, methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, methyl cellosolve or ethyl cellosolve etc.

There is no particular restriction for the solvent that uses in (A) operation and the match ratio of described metallic compound, with respect to the solvent of 10g, and the described metal oxide of preferred 0.1～100g.

The addition of the water that uses in (A) operation is preferably below 40 molar equivalents with respect to 1 mole of described metallic compound, more preferably below 10 molar equivalents, more preferably below 5 molar equivalents.

In addition, the catalyst that uses in this operation adds for the purpose that promotes described hydrolysis or polycondensation reaction.Such catalyst can use known catalyst, and (with reference to the large work in flat island, " up-to-date ゾ Le-ゲ Le method To よ ゐ Machine can do by the property film

Ji Intraoperative (utilizing up-to-date sol-gel process to make the technology of functional film) ", Co., Ltd. He Ji Intraoperative セ Application -(Co., Ltd. complex art center), p29 perhaps makes flower Ji husband work, " science of sol-gel process ", ア グ ネ holds wind person, p154 etc.).Comprise acid catalyst, base catalyst in these examples.Comprise inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, toluenesulfonic acid in the example of acid catalyst.

The example of base catalyst comprises alkali metal hydroxides such as ammonium hydroxide, potassium hydroxide, NaOH; Quaternary ammonium hydroxides such as TMAH, tetraethyl ammonium hydroxide, TBAH; Amines such as ammonia, triethylamine, tri-n-butylamine, morpholine, pyridine, piperidines, ethylenediamine, diethylenetriamines, monoethanolamine, diethanol amine, triethanolamine; 3-aminopropyltriethoxywerene werene, N (2-amino-ethyl)-amino silane classes such as 3-TSL 8330 etc.

Other example includes metal alkoxides such as machine tin compound, tetraisopropoxy titanium, bis-acetylacetonate base metatitanic acid diisopropyl ester, tetrabutyl zirconate, tetrem acyl acetone zirconium, aluminium isopropoxide, triethyl group pyruvic acid aluminium, trimethoxy borine etc.

Catalyst is preferably the following addition of 2 molar equivalents, more preferably below 1 molar equivalent with respect to 1 mole of described metallic compound.But, when described metallic compound has the functional group's (for example, amino or carboxyl etc.) that shows described catalytic action, preferably regulate the catalyst addition.

The gel-sol reaction exists hydrolysis, these two kinds of reactions of polycondensation reaction as previously mentioned, but each reaction is carried out simultaneously concurrently.Thereby, can not correspondingly with operation distinguish two reactions, but the former hydrolysis mainly take place in the initial reaction stage stage, the latter's reaction mainly takes place in the stage in reaction later stage.In addition, the process of carrying out of known two reactions of kind according to catalyst can be different.Usually, when using acid catalyst, hydrolysis carries out easily, and when using base catalyst, polycondensation reaction is carried out easily.

Sol gel reaction can wait by enforcement heating, microwave irradiation, infrared radiation and promote reaction.Thereby, in this (A) operation, amount that can be by water or catalyst, whether there are above-mentioned heater means, reaction time to wait to control the degree of carrying out of sol gel reaction.Along with the carrying out of sol gel reaction, the particle of metal oxide increases.Thereby the particle diameter of the metal oxide in the film that finally obtains is that the degree of carrying out by this sol gel reaction decides.

In the present invention, can mainly in film making process, control the particle diameter of metal oxide as described later.But preferred elder generation also regulates degree of reaction in basis (A) operation as its front operation.Owing to such reason, sol gel reaction in this operation preferably 0～150 ℃, further preferably 1～100 ℃, further preferably under 20～60 ℃, carry out, and preferably carry out further preferably carrying out about 1～30 hour about 1～50 hour.In the present invention, "～" uses with the meaning that comprises its two ends numerical value.The carrying out of reaction can be by mixture the rising of viscosity or appearance change such as muddiness confirm.

The B operation of (2) first methods

(B) of the present invention operation is that preparation is the solution (being called " resin solution ") of solute with the transparent resin.Said transparent resin is when thickness is 30 μ m, shows the organic polymer (polymer) of the parallel rays transmitance more than 70%.The transparent resin of Shi Yonging is preferably the water or the solvent that can mix with water is had deliquescent resin in the present invention.The example of such transparent resin comprises polyimides, Merlon, polyacrylate, polymethacrylates (PMMA), polyether-ketone, polyether-ether-ketone, polystyrene, polyester, epoxy resin, polyamide, polysulfones, Nomex, polyurethane, polyvinyl acetate, polyvinyl alcohol (PVA), polyacrylic acid.

Wherein, be preferably the polyimides that dissolves in the high solvent of boiling point and polarity, Merlon, polyacrylate, PMMA, polyether-ketone, polyether-ether-ketone, polystyrene, polyester etc.This is because the solvent that polarity is high and the compatibility of water are good, therefore as described later, carry out sol gel reaction easily in resin solution.In addition, if use high boiling solvent, then as described later, in the film making process of (D), control is scattered in the particle diameter of the metal oxide particle in the transparent resin etc. easily.Transparent resin can use separately, perhaps is used in combination.

In addition, when the occasion of the low resin of the occasion of using polyvinyl alcohol, this water-soluble transparent resin of polyacrylic acid or hear resistance,, preferably carry out crosslinked back and use for resistance to water or the hear resistance that improves the film that obtains.When using polyvinyl alcohol,, then can produce cross-linking reaction, thereby improve resistance to water if the resin that has a functional group with polyacrylic acid or polyamic acid etc. makes up, therefore preferred especially.Polyvinyl alcohol and polyacrylic cross-linking reaction are undertaken by heat treatment usually, in order to reduce treatment temperature, to shorten the processing time, also can use the esterification catalyst of putting down in writing among the PCT/JP2006/310193.

The solvent that uses in (B) operation gets final product so long as can dissolve the solvent of transparent resin, and unrestricted.Said solvent is meant the liquid substance of solubilized solute, can be organic solvent, also can be water.The example of such solvent is included in the solvent of narrating in aforesaid (A) operation.Is the identical solvent that maybe can mix particularly preferably in the solvent that uses in (B) operation with the solvent that uses in described (A) operation.

Preparation of the present invention is the operation of the solution of solute with the transparent resin, is to be undertaken by described transparent resin is dissolved in the described solvent.As required, can also heat or shine ultrasonic wave during dissolving.Also can buy commercially available is that the solution of solute is prepared with the transparent resin.The concentration of this solution is preferably 1～50 quality %, more preferably 5～30 quality %.

The C operation of (3) first methods

(C) of the present invention operation is that the mixture that will obtain in above-mentioned (A) operation mixes with the solution that obtains in (B) operation.There is no particular restriction for the method for mixing, and can carry out with stirrings such as mixers by be infused in the mixture that obtains in (A) operation in the solution that obtains in (B) operation.There is no particular restriction for the mixing ratio of this moment, preferably is adjusted to the amount that metal oxide in the blooming that finally obtains reaches expectation.

Also can be as required, after this (C) operation and before (D) operation, make the metallic compound that in the mixture that (C) operation obtains, exists carry out sol gel reaction (below, be called " appending reaction ").Append in the reaction can heat, microwave irradiation, infrared radiation etc.Preferably the reaction condition with described (A) operation is identical to append the condition of reaction, more preferably 20～60 ℃ of reactions about 1～30 hour down.

Append in the reaction described, also the material of from solvent, water, catalyst, selecting more than a kind be can mix again, this metallic compound and the sol gel reaction that is present in the metallic compound in the mixture that obtains by (C) operation from the beginning carried out.At this moment, if add again and the metallic compound different kinds of metals compound that is present in from the beginning in the mixture that obtains by (C) operation, then the refractive index of the metal oxide that contains in the blooming that finally obtains can be adjusted to the value of expectation, therefore preferred.In addition, in appending reaction,, then can also promote the polycondensation reaction of metallic compound if add base catalyst again.

(4) about (E) operation of second method

(E) operation is preferably similarly carried out with (B) operation of having narrated.Just, the solvent that uses in this (E) operation preferably can dissolve the metallic compound that uses in subsequent processing (F) operation.

(5) about (F) operation of second method

In this operation, what obtain in Xiang Zaiqian (E) operation is in the solution (resin solution) of solute with the transparent resin, mixes the metallic compound that generates metal oxide by sol gel reaction, carries out sol gel reaction.Same with aforementioned (A) operation, when having functional groups such as alkoxyl when metallic compound, selective hydrolysis and carry out polycondensation reaction after making hydroxyl.Therefore, it is also passable to add water as required.Further, it is also passable to contain catalyst in the water.

Above-mentioned reaction is for example by described metallic compound being dissolved in the resin solution that (E) operation obtains, and adds the water that can contain catalyst as required, in room temperature or be heated to set point of temperature and wait and carry out.At this moment, can use two or more metallic compounds.

The resin solution in this operation and the mixing ratio of described metallic compound are to be regulated such that the content of the metal oxide in the blooming that finally obtains as described above reaches the amount of expectation.Therefore the metallic compound that mixes in this operation is dissolved in the solvent easily owing to do not carry out sol gel reaction as yet, can directly be mixed in the resin solution.But, when metallic compound is difficult to be dissolved in resin solution, mix again after can being dissolved in solvent earlier.The solvent that use this moment preferably mixes with resin solution.

Condition (concentration of reaction system, temperature, time etc.) in this operation, preferred sol gel reaction, meeting is different with molecular weight because of the kind of the transparent resin of use, therefore cannot treat different things as the same.But when the concentration of resin solution was high, if in high reaction temperature or react for a long time, then the molecular weight of metal oxide increased, and has the possibility of high viscosityization or gelation.This be because, because the viscosity increased of resin solution, stir insufficiently, so sol gel reaction is carried out inhomogeneously easily.When the molecular weight of the transparent resin in the resin solution was big, the viscosity of resin solution also can rise, and therefore was easy to generate same phenomenon.Thereby it is 1～50 quality % that this reaction preferably makes the solid component concentration in the solution, and more preferably 5～30 quality % carry out.Described solid constituent is meant resin metallizing thing metal oxide.In addition, reaction temperature is preferably 0～150 ℃, more preferably 1～100 ℃, further is preferably 20～60 ℃.Reaction time was preferably about 1～50 hour, more preferably about 1～30 hour.

Further also can with (C) operation similarly, after (F) operation and before ensuing (G) operation, again mix by sol gel reaction generate metal oxide metallic compound, solvent, can contain the water of catalyst, carry out this metallic compound and the sol gel reaction of the metallic compound in the mixture that (G) operation obtains Already in.

Again the solvent that add this moment is preferably water, N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, DMSO, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, THF, diox, methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, methyl cellosolve or ethyl cellosolve.Described solvent can be identical with the solvent that uses in (E) operation, also can be different.

(6) control about the particle diameter of metal oxide

The particle diameter control of metal oxide can be undertaken by adjusting " drying condition in the film making process ", " interaction between transparent resin and the metal oxide ".About joint narration under being adjusted in the film making process, here the particle diameter control by " interaction between transparent resin and the metal oxide " is described.If strengthen the interaction of transparent resin and described metal oxide, then metal oxide is difficult for separating from resin, so the particle of metal oxide also diminishes.On the contrary, if reduce their interaction, then metal oxide particle increases.

In order to strengthen described interaction, increase the particle diameter of the metal oxide in the film, preferably use as metallic compound to have metal alkoxide, metal acetylacetonate compound, metal carboxylate, nitrate, oxychloride, the chloride that is easy to generate interactional functional group with transparent resin.The example that is easy to generate interactional functional group with transparent resin comprises amino, epoxy radicals, vinyl, acrylic, methacrylic acid group, NCO, sulfydryl etc.

Have the example that is easy to generate the metallic compound of interactional functional group with transparent resin and comprise vinyl trichlorosilane, vinyltrimethoxy silane, VTES, 3,4-epoxy radicals cyclohexyl ethyl trimethoxy silane, glycidoxypropyltrime,hoxysilane, the glycidoxy propyl-triethoxysilicane, the styryl trimethoxy silane, the methacryloxypropyl methyl dimethoxysilane, methacryloxypropyl trimethoxy silane, the methacryloxypropyl methyldiethoxysilane, the methacryloxypropyl triethoxysilane, the acryloxy propyl trimethoxy silicane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyldiethoxysilane, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330,2-aminoethylamino MTMS, 3-aminopropyl dimethylethoxysilane, 2-(2-amino-ethyl sulphur ethyl) triethoxysilane, the p-aminophenyl trimethoxy silane, N-phenyl-3-aminopropyl methyl dimethoxysilane, N-phenyl-3-aminopropyl methyldiethoxysilane, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the sulfydryl propyl trimethoxy silicane, sulfydryl propyl group methyl dimethoxysilane, NCO propyl-triethoxysilicane etc.

In addition, in order to improve the interaction of metal oxide and transparent resin, can in transparent resin, import the functional group that can form covalent bond, hydrogen bond, ionic bond etc.The example that can form the functional group of covalent bond comprises alkoxysilyl, silanol group etc.The example that can form the functional group of hydrogen bond comprises hydroxyl, carboxyl, amino etc.In addition, the example that can form the functional group of ionic bond comprises ammonium etc.

The object lesson that can reduce the particle diameter of metal oxide comprises transparent resins such as PMMA, PVA, polyamic acid or polyimides and the combination with metallic compound of amino, epoxy radicals.

On the contrary,, increase the particle diameter of the metal oxide in the film, preferably select transparent resin and metal oxide to be difficult for producing interactional combination in order to weaken the interaction of transparent resin and metal oxide.For example, preferably will have polar group transparent resin, with make up as the metal alkyl alkoxide with alkyl and alkoxyl of metallic compound.This is because because alkyl has hydrophobicity, the metallic compound that therefore has alkyl is difficult to affinity with the transparent resin with polar group, makes interaction between the two reduce.At this moment, further preferred with the solvent of water as resin solution, transparent resin then is water-soluble resin.For example, be that MTMS, transparent resin are polyvinyl alcohol (PVA) and polyacrylic acid (PAA), described solvent are that the example that is combined as of water describes with the metallic compound.The end of the metal oxide that is generated by MTMS has methyl.This methyl with partly be difficult to affinity as the water of solvent and the polarity of polyvinyl alcohol (PVA) and polyacrylic acid (PAA).Therefore, present the tendency of from transparent resin and solvent, separating easily.But on the other hand, the nonpolar part of this methyl and polyvinyl alcohol (PVA) and polyacrylic acid (PAA) has compatibility.Thereby, can not be fully from polyvinyl alcohol (PVA) and polyacrylic acid (PAA), separate, can keep the state that appropriateness is separated.Thereby, finally can be with the particle size adjustment of the metal oxide in polyvinyl alcohol (PVA) and the polyacrylic acid (PAA) size in certain degree.But the mechanism of particle diameter control is not defined in this.At this moment, described metal alkyl alkoxide preferably uses with other metallic compound (tetramethoxy-silicane etc.) is common.

, the particle diameter of the metal oxide in the blooming of the present invention can heterogeneity with respect to film thickness direction.This be because with blooming of the present invention when the optical diffusion film, can reduce the wavelength dependency of diffused light.The distribution of the particle diameter of metal oxide is as described below, can control by film making process.

1-2 film making process (D, G operation)

(D) of the present invention, (G) operation be, the mixture that will obtain in described operation (also comprise and carried out the described material that appends reaction) after coating on substrate or the container or launching, heats and solvent evaporated make film.In this operation, owing to when evaporating solvent, heat, so further carry out sol gel reaction sometimes.

Said expansion is meant, described mixture injected containers such as glass, metal, plastics, makes mixture be attached to wall of a container etc. by rotary container etc., makes mixture be shaped to membranaceous operation.This is shaped to the membranaceous mixture that contains solvent is called the film precursor.

Said coating is meant, is coated with roughly certain thickness to obtain the operation of film precursor on substrate etc. in described mixture.Said substrate is flat member, and the example of substrate comprises glass plate, polymeric membranes etc. such as the substrate, cylinder, band of glass, quartz, metal, pottery, plastics, rubber etc.Coating can adopt known method to carry out.The example of coating process comprises mobile rubbing method, infusion process, spraying process etc.At this moment, can use rod to be coated with machine, knife type coater, scraper plate coating machine, mould and be coated with known coating machines such as machine, comma formula coating machine, roll coater, intaglio plate coating machine, curtain coater, flush coater, spin coater.

In addition, also described mixture can be coated on the single or double of hyaline membrane, obtain as filming.In addition, also can be that coating fluid with described mixture and other kinds is coated on the multicoat membrane of making on the substrate.During as multicoat membrane system film, can set arbitrarily film is coated order on the hyaline membrane with the coating fluid of mixed liquor and other kinds.

In this operation, make the method for the solvent evaporation (drying) of the film precursor that carried out coating etc. adopt common heat drying stove to carry out.At this moment, also can reduce pressure, supply gas, processing such as infrared radiation, the irradiation of utmost point ultrashort wave.Drying can be carried out under air, inert gas atmosphere such as (nitrogen, argon gas).

(1) about the control of metal oxide particle

As previously mentioned, blooming of the present invention is preferably, and the metal oxide particle that is scattered in the film has " particle diameter gradient ".

The film with particle diameter gradient like this obtains by the drying condition optimization that makes this operation.This is because when the desciccator diaphragm precursor, the particle that produces the metal oxide that is caused by the carrying out of sol gel reaction is competitively grown up and is accompanied by the evaporation of the solvent in the film precursor and the reduction of the flowability brought.The optimum condition of this moment is different because of kind, the concentration of metal oxide, the solvent types of transparent resin, therefore, and the vague generalization difficulty.But, 1) and by selecting to make the slack-off condition of evaporation rate of the solvent in the film precursor, and 2) make metal oxide particle in the film precursor grow to the condition of certain degree, the particle diameter gradient that can obtain suiting by suitable selection.

At first, to 1) condition of the evaporation rate of solvent in the film precursor that slows down describes.Like this during the desciccator diaphragm precursor, can think the particle diameter gradient that causes metal oxide particle owing to following reason.

During with the state desciccator diaphragm precursor of the evaporation rate of the solvent that slows down, though the evaporation rate of the solvent of film integral body is slow, near the rapid solvent evaporation the air interface of film precursor (surface that contacts with air of film).So near the flowability the air interface of film precursor reduces, therefore be difficult to produce the reaction between the metallic compound, the growth of the metal oxide particle of this near interface just stops.On the other hand,, therefore, can not lose flowability, so metal oxide particle is just grown up because the evaporite ratio air interface of the solvent of film inside is slow.Therefore, the particle diameter of metal oxide of substrate interface side that is present in film is big, and the particle diameter of metal oxide that is present in the air interface side is little.In addition,, then also might increase the particle diameter of the metal oxide particle of film inside, reduce near the particle diameter of the metal oxide particle the two sides of film if improve the solvent permeability of the substrate of coated film precursor.

The condition that the evaporation rate of the solvent in the film precursor slows down is different because of concentration, the solvent types of the kind of transparent resin or metal oxide.But, preferred drying condition is: under 150 ℃ with film precursor quality after dry 1 hour, that remain in the solvent in the film precursor (below, be called " quality of 150 ℃ of remaining solvents after 1 hour "), be below 50 mass parts with respect to quality 100 mass parts of original solvent.Perhaps, preferred drying condition is: the quality of the quality of 100 ℃ of remaining solvents after 5 hours or the 50 ℃ remaining solvent after 10 hours is below 50 mass parts with respect to quality 100 mass parts of original solvent.

The evaporation rate of the solvent under the uniform temperature can be regulated boiling point by making up multiple solvent, or atmosphere reduced pressure regulates.In addition, can adopt ventilated drying oven etc. that atmosphere is under the gas flow.

Then, to 2) condition that makes metal oxide particle in the film precursor grow to certain degree describes.The baking temperature of this film making process is low more, and metal oxide particle is not just grown up more, and particle diameter integral body diminishes.This is because carrying out of the sol gel reaction of metallic compound is slack-off.The carrying out of sol gel reaction is slow, makes that sol gel reaction is not just carried out before growing to big particle diameter, and the metal oxide of therefore big particle diameter does not just exist yet.Thereby when baking temperature was low, the particle diameter gradient was also little.

On the other hand, when baking temperature was high, particle diameter is whole to become big.This is accelerating owing to sol gel reaction.And as previously mentioned, because near the evaporation of the solvent the air interface of film precursor accelerates, therefore the particle in the air interface side is difficult to grow up, but because the growth of the particle of substrate interface side is fast, its particle diameter gradient increase as a result.

When increasing baking temperature, the speed (programming rate) that its temperature is risen also impacts particle diameter and particle diameter distribution.Exist all the more fast programming rate particle diameter just big more, and the tendency that particle diameter reduces when slowing down programming rate.Because the evaporation rate of this phenomenon and solvent, the reaction speed of sol gel reaction, film is mobile closely related, therefore, is difficult to make the suitable combination vague generalization of temperature, programming rate, drying time.But if increase baking temperature or make programming rate too fast, then film can bubble.In addition, if reduce baking temperature or make programming rate slow excessively, then metal oxide particle is not too grown up.Thereby, grow to the size of certain degree in order to make metal oxide particle in the blooming, drying condition be preferably 40～180 ℃ dry 1～50 hour down.Wherein, baking temperature is preferably more than 60 ℃, more preferably more than 100 ℃.In addition, preferred programming rate is 0.1～25 ℃/minute, more preferably 0.1～15 ℃/minute, and more preferably 0.5～10/ minute.

In addition, the particle diameter of metal oxide also changes because of the boiling point of solvent.When baking temperature is identical since the boiling point of solvent the evaporation rate of high solvent is just slow more more, therefore as previously mentioned, the particle diameter gradient increases.In addition, when the evaporation rate of solvent was identical, because the high more then baking temperature of boiling point of solvent is just high more, therefore, the particle diameter of metal oxide and particle diameter gradient increased.As such solvent, preferred N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, cyclopentanone etc.

Above-mentioned condition preferably suitably adjusts to determine according to the structure of conceivable blooming, below, exemplify and can integrally increase particle diameter, and can increase the example of the particle diameter gradient on film thickness direction.

Transparent resin uses PMMA, PVA etc., and solvent uses the situation of NMP, DMAc:

The film precursor is warming up to about 120 ℃ from 50 ℃ with 0.5～10 ℃/minute speed, as required 120 ℃ of down dry a few hours.

Transparent resin uses the situation of polyamic acid:

The speed of film precursor with 0.5～10/ minute is warming up to about 180 ℃ from 50 ℃.Can further carry out the imidization reaction of polyamic acid 280～380 ℃ of following heat treatments.

Particle diameter integral body reduces and reduces when the particle diameter of film thickness direction distributes, and preferably with after the film precursor vacuum drying at room temperature of composition same as described above is about 5 hours, heats with above-mentioned condition and to carry out drying.

This (D) reaches (G), and operation preferably adopts the baking temperature of the good regulation of programming, the drying machine of programming rate to carry out.Perhaps, can prepare a plurality of drying machines such as baking oven that for example are set at set points of temperature such as 60 ℃, 90 ℃, 120 ℃ in advance, the film precursor all be put in each drying machine successively carried out drying in 5 minutes.At this moment, need heat up with 15 minutes and produce 60 ℃ temperature difference, so programming rate is 4 ℃/minute.

Blooming of the present invention is that the homogeneous mixture that contains transparent resin, solvent and metallic compound is made the film precursor, in this precursor metal oxide particle is grown up to obtain.Therefore, even the metal oxide particle in the film disperses with the form with particle diameter gradient, the volume fraction of the metal oxide on film thickness direction does not in fact change yet.That is, in film, be distributed with in the scope of the little metal oxide of particle diameter, the quantity of particle increases.On the other hand, in the scope that is distributed with the big metal oxide of particle diameter in film, the quantity of particle reduces.Therefore, blooming of the present invention has following advantage: the thermal coefficient of expansion on the thickness direction of film does not have difference, can be owing to variations in temperature etc. produces warpage.

(2) about the control of surface smoothing

According to the method that metal oxide particle merely is mixed in transparent resin reflex combination, if the size of metal oxide particle is that then film loses flatness more than the 1 μ m.This is because metal oxide particle is outstanding on the film surface.But manufacture method of the present invention is in described (D), (G) operation, the metal oxide particle of in the film precursor, growing up, so metal oxide particle can be not outstanding from the film surface.Thereby, be 1 μ m even be present in the size of the metal oxide particle in the film, also can obtain level and smooth film.

Similarly, then outstanding easily according to the method that metal oxide particle merely is mixed in transparent resin reflex combination at film surface metal oxide particle if increase the addition of metal oxide particle, so film loses flatness.But, even manufacture method of the present invention because this particle is outstanding on the film surface, therefore also can obtain level and smooth film according to the addition of aforementioned reason increase metal oxide.

In order to obtain the excellent especially film of surface smoothing, preferably be suppressed at the carrying out of the sol gel reaction of implementing before (D), (G) operation, the metal oxide particle of in (D), (G) operation, growing up.In order to slow down the carrying out of sol gel reaction, for example only use acid catalyst as catalyst, or reduce the use amount of catalyst, or reduce reaction temperature, or use reactive lower metallic compound, perhaps add acetic acid, acetylacetone,2,4-pentanedione or ethyl acetoacetate etc.

But, with regard to manufacture method of the present invention, even metal oxide particle is less than 1 μ m, if form the aggegation piece then also can damage the flatness on surface sometimes.At this moment, the preferably interaction that improves transparent resin and metal oxide as previously mentioned, the dispersiveness of improvement metal oxide.

The surface smoothing of film can scan the square scope of 200 μ m by the blooming surface being utilized AFM, measures centre plane roughness (Ra) and estimates.Said centre plane roughness (Ra) is will be " value that the absolute value of deviation that will be from datum level to given side averages " by the center line average roughness of JISB0601 definition in order to use and to be expanded to three-dimensional value the mensuration face.The surface smoothing of the blooming among the present invention is preferably below the 300nm in Ra, more preferably below the 100nm.This is because as previously mentioned, when blooming of the present invention and prismatic lens are used in combination, can suppress the damage to prismatic lens.

(3) about thickness

The adjusting of the thickness in the film making process can be adopted known method.For example, be coated with the gap of the instrument that machine etc. is used to be coated with, just can obtain expecting the film of thickness by suitable regulating rod.

(4) about other compositions

Manufacture method of the present invention can be added the additive corresponding with purpose in each operation.Comprise ultra-violet absorber, crosslinking agent, tackifier, filler, sensitizer, plasticizer, Photoepolymerizationinitiater initiater, monomer, oligomer, stabilizing agent, wetting agent, flowable, pigment, dyestuff, adhesion promoters, catalysts, dehydrating agent in the example of additive.

3. the purposes of blooming of the present invention

(1) particular optical rerum natura film

The total light transmittance of particular optical rerum natura film of the present invention is more than 70% and haze value is more than 20%.Therefore, what have is characterized as: the total light transmittance height, and to see through in the light be not parallelly to see through light but diffusion sees through the ratio height of light, that is, and and light diffusing height (light diffusing excellence).When the particle diameter that particularly is scattered in the metal oxide in this film is scattered in the film with the state with particle diameter gradient, can reduce the wavelength dependency of diffused light.

This particular optical rerum natura film can be the type (forward scattering) that diffusion sees through light, also can be the type (backscattering) of scattered reflection light.In addition, this particular optical rerum natura film also can be following type: to see through light and reverberation the two or in filming or the light of propagating in the film, produce the type that spreads.

Because such characteristic, this particular optical rerum natura film can be as light diffusing coating, the light diffusing film of optical applications.For example, can be as the light transmissive film of plastics or glass etc. or preventing dazzle or preventing to reflect the coating or the film of usefulness of thin plate, mirror, half mirror or known display element.

Further, particular optical rerum natura film of the present invention is suitable for display unit such as FPD.Specifically, be suitably used as the screen of the projecting display that uses display elements such as LCD, perhaps be used to improve the light diffusing sheet or the light diffusing reflector that distribute in the face of the briliancy of liquid crystal display cells or colourity.

In these FPD fields, especially require miniaturization and or reduce cost comprehensively, particular optical rerum natura film of the present invention can corresponding these requirements.For example, if use particular optical rerum natura film of the present invention to replace being used for the optical diffusion film of the sandwich construction of LCD, then, therefore help the slimming of display unit owing to can change multilayer film into monofilm.In such purposes, the preferred haze value of this particular optical rerum natura film is more than 70%, and Ra is below the 100nm, and thickness is below the 30 μ m.

Certainly, this particular optical rerum natura film is the purposes of the value below 70% for requiring haze value, also is suitable the use.

(2) gradient-structure film

Gradient-structure film of the present invention is that metal oxide is scattered in the blooming in the transparent resin, it is characterized in that on the thickness direction of this blooming, the particle diameter gradient of described metal oxide ground changes, and the volume fraction of this metal oxide does not change in fact.Therefore, the light diffusivity excellence of gradient-structure film of the present invention, and can reduce the wavelength dependency of diffused light, therefore also be suitable for the purposes of in above-mentioned particular optical rerum natura film, narrating.

In addition, when gradient-structure film of the present invention is used for the light taking-up of LED, inorganic EL or organic EL, but except diffused light, also can prevent the total reflection phenomenon that produces at the interface of transparent materials with different refractive index.

In addition, this gradient-structure film is, the metal oxide that is present in the substrate interface side is sub-micron～micron order, the metal oxide that is present in the air interface side is the structure that nanoscale disperses, therefore, also have following feature: the substrate interface side has light scattering effect, and the air interface side has light scattering effect hardly.Therefore, the blooming of unexistent function is of great use as having in the past.Such blooming has the average refractive index of transparent resin and metal oxide.

Embodiment

Below, the present invention will be described in more detail by embodiment, but the present invention is not limited to this.The below abbreviation among the expression embodiment.

DMAc: dimethylacetylamide

The NMP:N-N-methyl-2-2-pyrrolidone N-

TMOS: tetramethoxy-silicane

APTMOS: TSL 8330

GPTMOS: glycidoxypropyltrime,hoxysilane

MTMOS: trimethoxymethylsila,e

PMMA: polymethyl methacrylate

PVA: polyvinyl alcohol

PAA: polyamic acid

HCl: hydrochloric acid

HNO ₃: nitric acid

DCDA: dicyandiamide

NUC silicone L-7001: silicone-based levelling agent

TIPT: tetraisopropoxy titanium

M-BP:4,4 '-(3-amino-benzene oxygen) biphenyl

ODA:4,4 '-oxo diphenylamines (4,4 '-diaminodiphenyl ether)

PPD: p-phenylenediamine (PPD)

BPDA:3,3 ', 4,4 '-diphenyl tetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

Various mensuration among the embodiment are carried out as described below.

(optical detecting)

Adopt ultraviolet/visible spectrophotometer (manufacturing of UV3100PC/ (strain) Hitachi), measure parallel transmitance, total light transmittance and the reflectivity of blooming.Condition determination is as follows.

Measure wavelength: 300～1000nm, wavelength resolution: 1nm, mode determination: middling speed

In addition, adopt parallel transmitance and the total light transmittance of wavelength 550nm, calculate haze value by following formula.

Haze value (%)={ 1-(directional light transmitance/total light transmittance) } * 100

(mensuration of surface roughness)

Adopt table to go up small-sized probe microscope (manufacturing of Nanopics1000/ (strain) Seiko instrument), measure the center line average surface roughness Ra of blooming.Specifically, sweep limits is that 200 μ m are square, measures 5 subcenter line surface roughnesses, is tried to achieve by its mean value.

(scratching test)

The prismatic lens that 3cm is square (five foreign paper worker (strain) societies make, PC, 50 μ m spacings, height 21 μ m, drift angle 100 degree, the thick 240 μ m of sheet) is statically placed on the counter balance, makes prism facets towards upside.Place onesize blooming thereon, the face that becomes air interface when making the system film is in downside.Further on this film, place the square plate of 1cm, Yi Bian the square from it load that applies 10g, 20g, 50g, Yi Bian make this plate on blooming, do the reciprocating motion of 2cm.Then, take out prismatic lens, by the degree of injury of visual assessment thin slice.Fully not damage be evaluated as zero, can not confirm but available light microscope confirms to have the △ that is evaluated as of damage with range estimation, available range estimation confirm to have being evaluated as of damage *.

(the mensuration of metal oxide content: the thermogravimetric quantitative determination)

Adopt thermogravimetric amount determining device (TGA-50, Shimadzu Seisakusho Ltd.'s (strain) makes), heat blooming down at 30～800 ℃.Then, the residual ash amount in back of burning till under 800 ℃ is calculated metal oxide content.

(tem observation)

Behind epoxy resin embedding blooming, put in order with glass cutter, make ultra-thin section with diamond cutter then.The ultra-thin section of making is implemented carbon strengthen, adopt transmission electron microscope (TEM) (H-7000, the Hitachi makes), under accelerating potential 75kV, observe.

(measuring) by particle diameter, volume fraction that graphical analysis obtains

By the image that obtains by tem observation, adopt image analysis software (Image-Pro Plus:Planetron company) to obtain the area of metal oxide particle.Then, being obtained with the particle by calculating by the area of this particle is the diameter (circle equivalent diameter) of bowlder, calculates particle diameter.At this moment, calculate per unit area (the 25 μ m of the scope of the per 5 μ m on the thickness direction of film ²) average grain diameter, the average grain diameter X of the metal oxide particle that exists calculating from the substrate interface of film to the scope (X zone) of thickness 40%.Similarly, calculate from another side to same range as the average grain diameter Y of the metal oxide particle that exists (Y zone).Utilize X, the Y obtain like this, with X/Y as the particle diameter gradient.In addition, calculate per unit area (25 μ m in the X zone ²) the area occupation ratio W of particle, calculate the area occupation ratio V of the particle of the identical per unit area in the Y zone.Utilize this value, with W/V as volume fraction.

(mensuration of linear expansion coefficient)

Adopt thermo-mechanical analysis meter (TMA-50, Shimadzu Seisakusho Ltd. makes), apply certain load, the elongation (contraction) when measuring transformation temperature at the two ends of the length direction of film.Obtain the average coefficient of linear expansion (CTE) of 380～430 ℃ scope by measured value.

(determination of viscoelasticity: the mensuration of the storage modulus under 450 ℃)

The RSA-II that uses Rheometrics company to make, the temperature dispersion of the stretcher strain pattern of mensuration film is obtained the storage modulus E ' under 450 ℃.Condition determination be 30～500 ℃ of temperature ranges, 3 ℃/min of programming rate, Auto-Strain control down, deformation 0.02%, frequency 1Hz.In addition, sample is of a size of length 20mm, wide 5mm.

(embodiment 1) is operation (E): mix as the PMMA (1.0g) of transparent resin and NMP (4.0g) as solvent, prepare the PMMA/NMP solution 5g of 20 weight %.(F) operation: the PMMA/NMP solution 5g of the 20 weight % that will be obtained by (E) operation puts into the reaction vessel of 20ml.Then, the metallic compound that adds by sol gel reaction generation metal oxide is TMOS (1.0857g), the 0.1N HCl aqueous solution (0.5136g), at room temperature reacts 5 hours, so that the containing ratio of the metal oxide in the film that obtains is 30 weight %.0.1N the HCl aqueous solution adds after being diluted to 50 weight % with NMP.(G) operation: utilize Bake coating machine (Baker applicator) with the solution coat that obtains on glass substrate, make dry film thickness be approximately 35 μ m.Then, adopt inertia baking oven (inertoven), under the nitrogen atmosphere, be warming up to 120 ℃ from 50 ℃ with 3 ℃/minute programming rate, 120 ℃ dry 2 hours down.By such operation PMMA/ silica (Si oxide) composite membrane is made on the glass substrate.

Then, peel off above-mentioned film, obtain the PMMA/ silica composite membrane of thickness 35 μ m from glass substrate.The optical characteristics of the film that obtains is total light transmittance 91.0%, full light reflectance 7.3%, mist degree 35%.

(embodiment 2)

Use TMOS (0.6333g), the 0.1N HCl aqueous solution (0.2996g), so that the metal oxide containing ratio in the blooming is 20 weight %, in addition, the PMMA/ silica composite membrane of thickness 35 μ m is made in operation similarly to Example 1.The optical characteristics of the film that obtains is total light transmittance 92.0%, full light reflectance 75%, mist degree 24%.

(embodiment 3)

(E) operation: mix PMMA (1.0g) and DMAc (4.0g), the PMMA/DMAc solution of the 20 weight % of preparation 5g.

(F) operation: the PMMA/DMAc solution of the 20 weight % of the 5g that will be obtained by (E) operation is put into the reaction vessel of 20ml.Add TMOS (1.0748g), 0.1N HNO ₃The aqueous solution (0.5123g) at room temperature reacts 2 hours, so that the containing ratio of the metal oxide in the film that obtains is 30 weight %.0.1N HNO ₃The aqueous solution adds after being diluted to 50 weight % with DMAc.

Then, in described solution, add APTMOS (0.0128g), at room temperature reacted 2 hours.At this moment, APTMOS adds after being diluted to 10 weight % with DMAc again.

(G) operation: adopt solution coat that the Bake coating machine will obtain by above-mentioned operation on glass substrate, make dry film thickness be roughly 15 μ m.Then, adopt the inertia baking oven, under the nitrogen atmosphere, be warming up to 120 ℃ from 50 ℃ with 3 ℃/minute programming rate, 120 ℃ dry 2 hours down, PMMA/ silica composite membrane is produced on the glass substrate.

Then, peel off PMMA/ silica composite membrane, obtain the PMMA/ silica composite membrane of thickness 15 μ m from glass substrate.The optical characteristics of the film that obtains is total light transmittance 85.0%, full light reflectance 15.0%, mist degree 95.1%.

(embodiment 4～7)

With the condition shown in the table 1, PMMA/ silica composite membrane is made in operation similarly to Example 3.Specifically, use transparent resin, solvent, generate the metallic compound of metal oxide etc. by sol gel reaction according to the composition shown in the table 1, and the containing ratio of the metal oxide in the film that obtains is adjusted to 10,15,20,25 weight % makes film.Thickness, the optical characteristics of the film that obtains are shown in Table 1.

(embodiment 8)

(A) operation: TMOS (0.3800g), DMAc (0.3749g) are put into the reaction vessel of 10ml, add the 1.0N HCl aqueous solution (0.1798g), at room temperature reacted 3 hours.Separately TIPT (0.3559g) is put into the reaction vessel of 10ml, add acetic acid (0.3153g), at room temperature reacted 1 hour.Then, mix this two solution, at room temperature reacted 1 hour.

(B) operation: mix PMMA (1.0g) and DMAc (3.0g), the PMMA/DMAc solution of the 25 weight % of preparation 4g.

(C) operation: will mix with the solution that obtains by (B) operation by the solution that (A) operation obtains, at room temperature reacted 1 hour.Then, in this reactant mixture, add NUC silicone L-7001 (0.0250g), at room temperature stirred 10 minutes.NUC silicone L-7001 adds after being diluted to 10 weight % with DMAc again.

(D) operation: adopt solution coat that the Bake coating machine will obtain by above-mentioned operation on glass substrate, make dry film thickness be roughly 20 μ m.Then,, adopt the inertia baking oven, under the nitrogen atmosphere, be warming up to 120 ℃ from 50 ℃ with 3 ℃/minute programming rate for this glass substrate, 120 ℃ dry 2 hours down.Like this, the PMMA/ earth silicon/titanic oxide composite membrane with metal oxide containing ratio 20 weight %, earth silicon/titanic oxide=60 weight %/40 weight % is produced on the glass substrate.

Then, PMMA/ earth silicon/titanic oxide composite membrane is peeled off from glass substrate, obtained the PMMA/ earth silicon/titanic oxide composite membrane of thickness 20 μ m.The optical characteristics of the film that obtains is total light transmittance 91.0%, full light reflectance 9.5%, mist degree 92.4%.

(embodiment 9,10)

With the condition shown in the table 1, PMMA/ silica composite membrane is made in operation similarly to Example 8.Specifically, use transparent resin, solvent, generate the metallic compound of metal oxide etc. by sol gel reaction, and the containing ratio of the metal oxide in the film that obtains is adjusted to 15,10 weight % obtains film according to the composition shown in the table 1.Thickness, the optical characteristics of the film that obtains are shown in Table 1.

(embodiment 11)

(A) operation: the reaction vessel with MTMOS (1.17g) puts into 10ml adds 0.06N HNO ₃The aqueous solution (0.46g) at room temperature reacted 1 hour 30 minutes.

(B) operation: PVA (0.3g), PAA (0.71g) are put into the reaction vessel of 10ml, add pure water (1.9g), DCDA (0.172g), at room temperature stirred 15 minutes.

(C) operation: will mix with the solution that obtains in (B) operation at the solution that (A) operation obtains, at room temperature reacted 1 hour.

(D) operation: use the solution of the disk filter filtration gained of aperture 1 μ m, adopt the Bake coating machine that filtrate is coated on the PET film of thickness 110 μ m, make dry film thickness be roughly 24 μ m.Then, with at room temperature dry 10 minutes of this PET film, adopt convection oven 40 ℃ dry 10 minutes down, 120 ℃ dry 1 hour down.Like this, the PVA/PAA/ silica composite membrane with metal oxide containing ratio 33 weight % is produced on the PET film.The optical characteristics of the film that obtains is as shown in table 2, total light transmittance 88.5%, full light reflectance 10.6%, mist degree 91.7%.Ra is 88nm.

(embodiment 12～15)

With the condition shown in the table 2, PVA/PAA/ silica composite membrane is made in operation similarly to Example 11.Specifically, use transparent resin, solvent, generate the metallic compound of metal oxide etc. by sol gel reaction according to the composition shown in the table 2, and the containing ratio of the metal oxide in the film that obtains is adjusted to 10,15,20,25 weight % makes film.The results are shown in the table 2 of the thickness of the film that obtains, optical characteristics, Ra and scuffing test.

(comparative example 1)

Mix PMMA (1.0g) and DMAc (4.0g), the PMMA/DMAc solution of the 20 weight % of preparation 5g.The PMMA/DMAc solution of the 20 weight % of the 5g that obtains is put into the reaction vessel of 20ml, add SiO ₂Particle (0.4285g, space portion day east changes into society and makes, trade name Hipresica TS, average grain diameter 5.0 μ m) is so that the containing ratio of the metal oxide in the film that obtains is 30 weight %.After this solution at room temperature stirred 1 hour, handled 1 hour with ultrasonic wave.Adopt the Bake coating machine with the solution coat that obtains on glass substrate, make dry film thickness be roughly 14 μ m.Then,, adopt the inertia baking oven, under the nitrogen atmosphere, be warming up to 120 ℃ from 50 ℃ with 3 ℃/minute programming rate for this glass substrate, 120 ℃ dry 2 hours down.Like this, with PMMA/SiO ₂The particle composite membrane is produced on the glass substrate.

Then, peel off PMMA/SiO from glass substrate ₂The particle composite membrane obtains the PMMA/SiO of thickness 14 μ m ₂The particle composite membrane.The optical characteristics of the film that obtains is total light transmittance 89.9%, full light reflectance 7.1%, mist degree 52.6%.Ra is 498nm.Scratch the result of test, under the condition of load 10g, produced the damage that available range estimation is confirmed on the prismatic lens.

(comparative example 2)

PVA (0.3g), PAA (0.71g) are put into the reaction vessel of 10ml, add pure water (1.9g), DCDA (0.172g), at room temperature stirred 15 minutes.Further add SiO ₂Particle (0.4975g, space portion day east changes into society and makes, trade name Hipresica TS, average grain diameter 5.0 μ m) is so that the containing ratio of the metal oxide in the film that obtains is 33 weight %.This mixture was at room temperature stirred 1 hour, handled 1 hour with ultrasonic wave then.Adopt the Bake coating machine that the mixture that obtains is coated on the PET film of thickness 110 μ m, make dry film thickness be roughly 16 μ m.With at room temperature dry 10 minutes of this PET film, adopt convection oven 40 ℃ dry 10 minutes down, 120 ℃ dry 1 hour down, with the PVA/PAA/SiO of metal oxide containing ratio 33 weight % ₂The particle composite membrane is produced on the PET film.

The film that obtains is carried out the result of optical detecting, total light transmittance 86.2%, full light reflectance 11.8%, mist degree 88.0%.The result who measures surface roughness Ra is 720nm.Scratch the result of test, under the condition of load 10g, produced the damage that available range estimation is confirmed on the prismatic lens.

By embodiment 1～15 and comparative example 1～2 as can be known, the blooming that obtains with manufacture method of the present invention, with silicon dioxide granule merely is mixed in transparent resin film compare, thickness approaches, optical characteristics, surface smoothing excellence.Further as can be known, when being used in combination, do not damage this sheet substantially with prismatic lens.

(synthesis example 1)

In the container that possesses mixer and nitrogen ingress pipe, put into DMAc 261.0g as solvent, further add ODA 20.44g, m-BP16.12g, stir down at 20～30 ℃ and dissolve.Then, in same container, add PMDA 30.84g, wash the raw material that falls to being attached to flask interior with the DMAc of 11.0g.Then, reaction system is heated to 50～60 ℃, carries out about 1 hour stirring.Then, in this reactant mixture, add PMDA 0.44g, on one side temperature is remained in 60 ℃, carry out about 4 hours stirring on one side, obtain varnish 1.

Then, possess in the container of mixer and nitrogen ingress pipe, put into NMP263.0g, further add PPD 19.62g, stir down at 20～30 ℃ and dissolve as solvent to another.Then, add BPDA37.0g, PMDA 11.06g, wash the raw material that falls to being attached to flask interior with the NMP of 10.0g.Then, reaction system is heated to 50～60 ℃, carries out stirring in about 4 hours, obtain varnish 2.

Then, possess in the container of mixer and nitrogen ingress pipe, put into described varnish 1 and 2, be heated to 50～60 ℃, carry out stirring in about 4 hours, obtain the polyamide-based acid solution with the weight ratio of 77:23 to another.In this polyamide-based acid solution, the containing ratio of polyamic acid is 20 weight %, and the E type viscosity under 25 ℃ is 30000mPas.Is 10ppm/ ℃ by this polyamic acid by the linear expansion coefficient that common method obtains polyimide film.

(embodiment 16)

Polyamic acid/NMP-DMAc solution (polyamic acid 15 weight %) 18g that will be obtained by synthesis example 1 puts into the reaction vessel of 100ml, adds TMOS (1.378g), water (0.652g), 60 ℃ of reactions 6 hours down.TMOS, water are to add after being diluted to 50 weight % with NMP again.The solution coat that employing Bake coating machine will obtain like this makes dry film thickness be roughly 16 μ m on Copper Foil.Then, for this Copper Foil, adopt the inertia baking oven, the programming rate with 3 ℃/minute under the nitrogen atmosphere is heated to 180 ℃ of next dryings from 50 ℃.Then, adopt the IR reflow ovens to carry out 280 ℃ to 380 ℃ heat treatment, the polyimide/silicon dioxide composite membrane is produced on the Copper Foil.

For described Copper Foil, handled about several minutes from jet printing type nozzle ejection ferric chloride solution (40 Baume degrees), remove Copper Foil and obtain the polyimide/silicon dioxide composite membrane.Then, wash this film,, obtain the polyimide/silicon dioxide composite membrane of thickness 16 μ m 60 ℃ of following vacuum drying.

The TEM image of the film that obtains is shown among Fig. 1, carries out graphical analysis and particle diameter, the volume fraction of trying to achieve are shown in Table 4 by the TEM image.By the observed appearance of Fig. 1 be: the silica of Copper Foil side is grown into the particle shape, and the silica of air interface side is nano-dispersed.In addition, the gained film is measured the dioxide-containing silica get by TGA and is shown in Table 3, and the elastic modelling quantity under the CTE (linear expansion coefficient), 450 ℃ is shown in Table 4.

(embodiment 17)

Polyamic acid/NMP-DMAc the solution that to make in synthesis example 1 (polyamic acid 15 weight %) 18g puts into the reaction vessel of 100m1, adds TMOS (1.378g), water (0.652g), reacts 1 hour down at 60 ℃.Then, adding in this solution and containing amino alkoxy silane is APTMOS (0.0016g), 60 ℃ of reactions 5 hours down, obtains being dispersed with the solution of the polyamide-based acid composition of silica.TMOS, APTMOS, water are to add after being diluted to 50 weight % with NMP again.By the solution that obtains like this, the polyimide/silicon dioxide composite membrane of thickness 16 μ m is made in operation similarly to Example 16.The gained film is shown in Table 4 by particle diameter, the volume fraction of the silica that the TEM image is tried to achieve.In addition, the gained film is measured the dioxide-containing silica try to achieve by TGA and is shown in Table 3, and the elastic modelling quantity under 450 ℃ is shown in Table 4.

(embodiment 18,19)

Operate similarly to Example 17 with the condition shown in the table 3, obtain being dispersed with the solution of the polyamide-based acid composition of silica.Then, by this solution, operation similarly to Example 16, the polyimide/silicon dioxide composite membrane of making thickness 16 μ m.Particle diameter, the volume fraction of the silica of the film that obtains are shown in Table 4.The dioxide-containing silica of being tried to achieve by TGA mensuration of the film that obtains in addition, is shown in Table 3.

(embodiment 20)

Adopt the Bake coating machine, on Copper Foil, make dry film thickness be roughly 16 μ m the solution coat of operating similarly to Example 16 and obtaining.Then, adopted at room temperature dry this Copper Foil of vacuum drier 5 hours, further adopt the inertia baking oven, under the nitrogen atmosphere, be heated to 180 ℃ from 50 ℃ and carry out drying with 3 ℃/minute programming rate.Then, adopt the IR reflow ovens, this Copper Foil is carried out 280 ℃ to 380 ℃ heat treatment, the polyimide/silicon dioxide composite membrane is produced on the Copper Foil.

To the Copper Foil ferric chloride solution (40 Baume degrees) of jetting, the processing of carrying out about several minutes is until the Copper Foil complete obiteration with the jet printing type nozzle.After the film water that obtains washed,, obtain the polyimide/silicon dioxide composite membrane of thickness 16 μ m 60 ℃ of following vacuum drying.The particle diameter of the silica of the film that obtains is shown in Table 4.In addition, the dioxide-containing silica of being tried to achieve by TGA mensuration of film is shown in Table 3.

(embodiment 21)

Polyamic acid/NMP-DMAc the solution that to make in synthesis example 1 (polyamic acid 15 weight %) 18g puts into the reaction vessel of 100ml, adds TMOS (1.282g), water (0.650g), reacts 1 hour down at 60 ℃.Then, adding the alkoxy silane that contains epoxy radicals is GPTMOS (0.1873g), reacts 5 hours down at 60 ℃, obtains the solution of silica disperse polyamides base acid composition.TMOS, GPTMOS, water are to add after being diluted to 50 weight % with NMP again.Use the solution that obtains like this, the polyimide/silicon dioxide composite membrane of thickness 16 μ m is made in operation similarly to Example 16.The particle diameter of the silica of the film that obtains is shown in Table 3, and measures the dioxide-containing silica of trying to achieve by TGA and is shown in Table 4.

(comparative example 3)

By the polyamic acid/NMP-DMAc solution (polyamic acid 12.5 weight %) of synthesis example 1, the polyimide film of thickness 16 μ m is made in operation similarly to Example 16.The measuring the dioxide-containing silica try to achieve by TGA and be shown in Table 3 of the film that obtains, the elastic modelling quantity under the CTE (linear expansion coefficient), 450 ℃ is shown in Table 4.

(comparative example 4)

With cataloid/DMAc solution (silica 20 weight %) 2.690g, join among polyamic acid/NMP-DMAc solution (polyamic acid 15 weight %) 18g of synthesis example 1, stirred 5 hours down at 60 ℃, obtain the solution of polyamide-based acid composition.By the polyamide-based acid solution that obtains, the polyimide/silicon dioxide composite membrane is made in operation similarly to Example 16.The particle diameter of the silica of the film that obtains is shown in Table 4.In addition, the measuring the dioxide-containing silica try to achieve by TGA and be shown in Table 3 of the film that obtains, the elastic modelling quantity under 450 ℃ is shown in Table 4.

Can confirm that with comparative example 3～4 blooming of the present invention is that silicon dioxide granule is scattered in the transparent resin with the state with particle diameter gradient, and the volume fraction of film thickness direction is below 2 by embodiment 16～21 on film thickness direction.In addition, by the value of elastic modelling quantity and CTE as can be known, dimensional stability and the mechanical property excellence of blooming of the present invention in high-temperature area.

(the affirmation tests of embodiment 22 index modulation effects)

Near the reflectivity air interface of the polyimide/silicon dioxide complex of embodiment 16, the position of silicon dioxide granule nano-dispersed in polyimide film is measured.At first, the polyamic acid/NMP-DMAc solution that will make in synthesis example 1 (polyamic acid 15 weight %) 18g puts into the reaction vessel of 100ml, adds TMOS (1.838g), water (0.652g), reacts 1 hour down at 60 ℃.Then, adding and containing amino alkoxy silane is APTMOS (0.1505g), reacts 5 hours down at 60 ℃, obtains the solution of silica disperse polyamides base acid composition.TMOS, APTMOS, water are to add after being diluted to 50 weight % with NMP again.

By the solution that obtains, the polyimide/silicon dioxide composite membrane of thickness 16 μ m is made in operation similarly to Example 16.The film that obtains is carried out tem observation, confirm that near the structure the air interface of this film is identical with the film of embodiment 16.The result of reflectivity who measures the wavelength 550nm place of this film is, reflectivity is 10.58%, and the refractive index of being obtained by reflectivity is 1.61.

In addition, by the polyamic acid/nmp solution (polyamic acid 12.5 weight %) of synthesis example 1, polyimide film is made in operation similarly to Example 16.The reflectivity of the film of making is 11.17, and the refractive index of being obtained by reflectivity is 1.63.Promptly can know,, can see that refractive index reduces by the silica of refractive index 1.46 is added polyimides, in the nano-dispersed side of the silicon dioxide granule of embodiment 16, but refraction index modulation.

(embodiment 23)

With fluorine modified polyamide base acid/DMAc solution (optics that Hitachi Chemical Co., Ltd. makes polyimides " OPI ", polyamic acid 25 weight %) 6g, put into the reaction vessel of 20m1, add TMOS (0.911g), water (0.432g), at room temperature reacted 5 hours.Water is to add after being diluted to 50 weight % with DMAc again.Adopt the Bake coating machine with the polyamic acid solution coat that obtains on glass substrate, make dry film thickness be roughly 50 μ m.Then,, adopt the inertia baking oven, come to carry out imidization reaction in dry being warming up to 330 ℃ under the nitrogen atmosphere from 50 ℃ with 3 ℃/minute programming rate, make the polyimide/silicon dioxide composite membrane for this glass substrate.This film can easily be peeled off from glass substrate.The film that obtains is carried out tem observation, confirm to contain the particle that particle diameter changes on film cross-wise direction gradient ground.In addition, the particle diameter of the silica that is obtained by graphical analysis is shown in Table 5.The mist degree at the wavelength 550nm place of this film is 96%.

With the polyolefin plate (manufacturing of TPXR/ Mitsui Chemicals, Inc) of adhering, the film that obtains is attached on the surface of opposition side of formation anode of transparency carrier of organic electroluminescent planar luminous body (manufacturing of IMES company) as the light diffusion part.Then, this planar luminous body is connected in power supply (manufacturing of PA36/ K.K. Kenwood), when applying 0.27A/32V, measures 3000cd/m ²Positive briliancy and inclined to one side 45 the degree briliancy.Measure and adopt brightness photometer (manufacturing of BP6/ Topcon Co., Ltd).

The briliancy of this device can be confirmed to compare when not being provided with the light diffusion part, and positive briliancy improves 1.2 times, and inclined to one side 45 degree briliancy improve 1.3 times.

Table 5

Applicability on the industry

Blooming of the present invention is owing to the light diffusing excellence, be film and surface smoothness excellence, therefore Be applicable to the field of optical diffusion film etc.

The application advocates priority based on the application number JP2006-076767 of application on March 20th, 2006 and the application number JP2006-334374 of application on December 12nd, 2006.The content of putting down in writing in this application specification is all quoted by present specification.

Claims (20)

1. the manufacture method of a blooming is characterized in that, comprising: (A) will generate the metallic compound of metal oxide by sol gel reaction, and carry out the operation of sol gel reaction in solvent; (B) preparing with the transparent resin is the operation of the solution of solute; (C) mixture that will in described (A) operation, the obtain operation of mixing with the solution that in (B) operation, obtains; And the mixture that (D) will obtain in described (C) operation is after coating on substrate or the container or launching, and heats the operation that solvent is evaporated form film, and the total light transmittance of this blooming is more than 70%, and haze value is more than 20%.

2. the manufacture method of blooming according to claim 1 is characterized in that, before described (D) operation, further comprises and makes the described metal oxide that exists in the mixture that obtains in (C) operation carry out the operation of sol gel reaction.

3. the manufacture method of a blooming is characterized in that, comprising: (E) preparing with the transparent resin is the operation of the solution of solute; (F) in the solution that in described (E) operation, obtains, mix the metallic compound that generates metal oxide by sol gel reaction, and carry out the operation of sol gel reaction; And the mixture that (G) will obtain in described (F) operation is after coating on substrate or the container or launching, and heats the operation that solvent is evaporated form film, and the total light transmittance of this blooming is more than 70%, and haze value is more than 20%.

4. the manufacture method of blooming according to claim 3, it is characterized in that, before described (G) operation, further comprise in the mixture that in (F) operation, obtains, mixing generates metallic compound, solvent, water or the catalyst of metal oxide by sol gel reaction, and carries out the operation of sol gel reaction.

5. according to the manufacture method of claim 1 or 3 described bloomings, it is characterized in that described (D) or film making process (G) comprise the operation of the particle growth that makes the metal oxide that is generated by described sol gel reaction.

6. the manufacture method of blooming according to claim 5 is characterized in that, the operation that the described particle that makes metal oxide is grown up is to make described particle diameter change the operation of growing up with respect to the thickness direction gradient ground of described blooming.

7. according to the manufacture method of claim 1 or 3 described bloomings, it is characterized in that described transparent resin is polyimides, Merlon, polyacrylate, polymethacrylates, polyether-ketone, polyether-ether-ketone, polystyrene, polyester, epoxy resin, polyamide, polysulfones, Nomex, polyurethane, polyvinyl acetate, polyvinyl alcohol or polyacrylic acid.

8. according to the manufacture method of claim 1 or 3 described bloomings, it is characterized in that described metallic compound by sol gel reaction generation metal oxide comprises silicon, titanium, zirconium or aluminium element.

9. according to the manufacture method of claim 1 or 3 described bloomings, it is characterized in that described metallic compound by sol gel reaction generation metal oxide is metal alkoxide, metal acetylacetonate compound, metal carboxylate or their condensation polymer.

10. want the manufacture method of 1 or 3 described bloomings according to right, it is characterized in that, in described sol gel reaction,, use inorganic acid, organic acid, inorganic base or organic base as catalyst.

11. the manufacture method according to claim 1 or 3 described bloomings is characterized in that, described (D) operation or (G) operation be 40～180 ℃ of following heating operations of coming evaporating solvent in 1～50 hour.

12. manufacture method according to claim 1 or 4 described bloomings, it is characterized in that, solvent that uses in described (A) operation or the solvent that is mixed in the mixture that obtains in described (F) operation are water, N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, DMSO, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, THF, diox, methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, methyl cellosolve or ethyl cellosolve.

13. manufacture method according to claim 1 or 3 described bloomings, it is characterized in that, described metallic compound by sol gel reaction generation metal oxide is included in the metal alkyl alkoxide that has alkyl and alkoxyl in the molecule, and described is that the solvent of the solution of solute comprises water with the transparent resin.

14. the manufacture method according to claim 1 or 3 described bloomings is characterized in that described blooming is an optical diffusion film.

15. a blooming that produces by claim 1 or 3 described methods is characterized in that thickness is below the 30 μ m, and haze value is more than 70%.

16. blooming according to claim 15 is characterized in that, the centre plane roughness (Ra) of single or double is below the 100nm.

17. blooming, it is scattered in blooming in the transparent resin for metal oxide, it is characterized in that, on the thickness direction of this blooming, the particle diameter gradient ground of described metal oxide changes, and the volume fraction of this metal oxide does not change in fact.

18. blooming according to claim 17, it is characterized in that, when the average grain diameter that is present in from a face to the per unit area of the described metal oxide of the scope of thickness 40% of described blooming is X, the average grain diameter of the per unit area of the described metal oxide of 40% scope is Y from another face to thickness, and when X was bigger than Y, the particle diameter gradient that defines with X/Y was more than 1.2.

19. blooming according to claim 17, it is characterized in that, when the volume fraction that is present in from a face to the described metal oxide of the scope of thickness 40% of described blooming is W, 40% volume fraction with the described metal oxide of interior scope is V from another face to thickness, and W is V when above, is below 2 with the volume fraction gradient of W/V definition.

20. blooming according to claim 17 is characterized in that, described blooming is an optical diffusion film.

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